KR960015370B1 - Cleaning and washing composition - Google Patents

Abstract

None.

Description

Cleaning and cleaning agents

The present invention relates to an aqueous cleaning and cleaning agent containing 2 to 25% by weight of β-alanine-N, N-diacetic acid or an alkali metal or an ammonium salt thereof as an emollient of water, based on the total weight of the cleaning and cleaning agent. will be.

Aqueous cleaning and cleaning agents are generally made by combining various surfactants and other auxiliaries.

Other auxiliaries are, among other things, softeners, i.e. substances capable of binding light water ions, in particular Ca ²⁺ , Mg ²⁺ cations.

The softeners of water used so far are mainly phosphates, which are increasingly undesirable due to environmental aspects. New phosphate substitutes include nitrilotriacetic acid and salts thereof, but likewise these compounds are not very satisfactory because they are not effective enough, for example, to remove cure deposits on fabrics.

It is an object of the present invention to provide aqueous washing and cleaning agents which contain a softener of water that is much more effective than nitrilotriacetic acid.

The inventors have found that this object is achieved by an aqueous cleaning and cleaning agent containing 2 to 25% by weight of β-alanine-N, N-diacetic acid or an alkali metal or an ammonium salt thereof as an emollient of water based on the total weight of the reagents. Found to be achieved.

Like nitrilotriacetic acid, β-alanine-N and N-diacetic acid are decomposed into microorganisms and are particularly advantageously prepared by reacting acrylic acid with aminodiacetic acid in an aqueous medium (see, Federal Republic of Germany Patent Application No. P38 29 859.7-). OZ 0050/40154).

Additional advantages of β-alanine-N, N-diacetic acid are presented by comparing the corresponding equilibrium constants (pages 564 and 565 of Organic Sequestering Agents, AE Martell, J. Wiley & Sons, New York (1959)). As one has, its low binding capacity (compared to nitriloacetic acid) to heavy metal ions such as Cu ²⁺ or Cd ²⁺ . This reduces the likelihood that heavy metal ion deposits in the sediment of the steel are resuspended by small amounts of undecomposed β-alanine-N, N-diacetic acid.

Based on the total weight of the cleaning and cleaning agent according to the invention, β-alanine-N, N-diacetic acid or an alkali metal or ammonium salt thereof is used in an amount of 2 to 25, preferably 5 to 15% by weight. It is particularly advantageous to use alkali metal salts thereof, of which trisodium salt is particularly preferred. However, β-alanine-N, N-diacetic acid together with basic compounds such as primary, secondary tertiary aliphatic organic amines having 1 to 4 carbon atoms in aliphatic groups such as potassium hydroxide, ammonia or methylamine, dimethylamine, or trimethylamine It is also possible to use salts.

The remaining constituents of the cleaning and cleaning agents according to the invention depend on the specific intended use.

Generally, the cleaning agent is 5 to 50% by weight of other water softeners, 6 to 25% by weight of other water softeners as active detergent, 6 to 25% by weight surfactant as active detergents, 5 to 35% by weight bleach of preparation 0 to 60% by weight of the main substance for consistency and, moreover, small amounts of auxiliaries such as bleach stabilizers, bleach activators, enzymes, gray inhibitors, foam control agents, antiseptics, fluorescent bleaches, solubilizers, fragrances and dyes. .

In general, the cleaning agent is also a main component, immersing 30 to 80% by weight of the time, 3 to 20% by weight of other reagents capable of binding hard water ions, 2 to 10% by weight of surfactant, 1 to 5% by weight of Antiseptics, containing 0 to 60% by weight of the main substance for consistency of production and even smaller amounts of auxiliaries such as enzymes, foam control agents, flavorings, solubilizers or disinfectants.

Additional Ca ^{2+ -and} Mg ²⁺ -binding aids added to the cleaning and cleaning agents according to the invention are sodium carbonate, sodium silicate and sodium phosphate or inorganic complex reagents such as pyrophosphate, triphosphate, higher poly Phosphates and metaphosphates, or suitable from alkal-polyphosphoric acid, amino- and hydroxy-alkalipolyphosphoric acid, phosphonocarboxylic acid, polycarboxylic acid, hydroxymono- or -polycarboxylic acid and aminocarboxylic acid There is an organic complex, and preferably, an ion exchange material such as sodium aluminum silicate (zeolite), and the complex acid thereof in the form of their water solubility are preferably used for the cleaning agent.

Examples of suitable phosphorus-containing organic complexing agents include methanediphosphonic acid, propane-1, 2, 3-triphosphonic acid, butane-1, 2, 3, 4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane -1, 1-diphosphonic acid, 1-amino-1-phenyl-1, 1-diphosphonic acid, aminotrimethylenephosphonic acid, methylamino or ethylamino-dimethylenediphosphonic acid ethylenediaminotetramethylenetetraphosphone Acids, 1-hydroxyphosphonopropionic acid, 1-phosphonoethane-1, 2-dicarboxylic acid, 2-phosphonopropane-2, 3-dicarboxylic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 2-phosphonobutane-2, 3, 4-tricarboxylic acid and copolymers of vinylphosphonic acid and acrylic acid.

을 갖는 아크릴산(AA) 및 말레산(MA)의 공중합체가 특히 바람직하며, 또한 당, 전분 및 셀룰로오스의 카르복시메틸에테르도 있다.Examples of polycarboxylic acids include dicarboxylic acids of the general formula HOOC- (CH ₂ ) _n -COOH, wherein n is 0 to 8, and also maleic acid, itaconic acid, at least 3 carboxyl in the molecule. Acyclic polycarboxylic acids having groups, ie tricarblylic acid, aconic acid, ethylenetetracarboxylic acid, 1, 1, 3, 3-propanetetracarboxylic acid, 1, 1, 3, 3, 5, 5 Pentane hexacarboxylic acid, hexane hexacarboxylic acid, cyclic di- or polycarboxylic acid, ie cyclopentanetetracarboxylic acid, cyclohexanehexacarboxylic acid, tetrahydrofuranthratecarboxylic acid, phthalic acid, terephthalic acid, Benzenetri-, -tetra- or pentacarboxylic acid, melic acid and polymeric polycarboxylic acids, ie homopolymers of acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconic acid, methylenemalonic acid and sheets Laconic acid, with carboxylic acids mentioned above or ethylene, Copolymers with ethylenically unsaturated compounds such as propylene, isobutylene, vinylalcohol, vinylmethylether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile, methacrylic acid and crotonic acid, in which case , Average molecular weight of 70,000 in weight ratio of 60: 40

Particularly preferred are copolymers of acrylic acid (AA) and maleic acid (MA) having a carboxymethyl ether of sugar, starch and cellulose.

Suitable hydroxymono- or -polycarboxylic acids include glycolic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconsinglyceric acid, citric acid, tartaric acid and salicylic acid.

Preferred aminocarboxylic acids include glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, aminodiacetic acid, aminotriacetic acid, hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid , Which can be prepared by copolymerization (reaction) and subsequent hydrolysis (reaction) of diethylenetriaminepentaacetic acid and N-aziridylcarboxylic acid derivatives such as acetic acid, succinic acid or tricarvallylic acid or of 500 to 10,000 There are higher homologues which can be prepared by condensation (reaction) of a polyamine having a molecular weight with a salt of chloroacetic acid or bromoacetic acid.

Suitable ion exchange materials are, in particular, zeolite 4A, the preparation of which is described in Ullmanns Encyclopadie der technischen Chemie, 4th edition, Volume 24, page 10.

Suitable surfactants include those containing one or more hydrophobic organic residues and ionic or nonionic groups dissolved in water in the molecule. The hydrophobic residue is preferably an aliphatic hydrocarbon having 8 to 26, preferably 10 to 22, particularly preferably 12 to 18, or an alkylaromatic group having 6 to 18, preferably 8 to 16 carbon atoms in the alkyl group. .

Particularly suitable anionic surfactants are the sodium, potassium and ammonium salts of carboxylic acids having the above mentioned number of carbon atoms, sulfonic acids, and monoester sulfates.

Among these, suitable surfactants in the form of sulfonates include, in particular, alkylbenzenesulfonates having 9 to 15 carbon atoms in the alkyl group, alkenes and hydroxylalkane-sulfonates and monoolefins having double bonds at the terminals or inside, for example. There are silver disulfonates and those obtained by sulfonation (reaction) with sulfur trioxide and continuous alkali or acid hydrolysis (reaction). In addition, alkanesulfonates which can be obtained by alkanol chlorosulfonation (reaction) or sulfoxylation (reaction) and subsequent hydrolysis (reaction) or neutralization (reaction) or by addition (reaction) of hydrogen sulfite to olefins (reaction). It is also possible to use. Even more useful surfactants in the form of sulfonates are methyl and ethyl esters of α-sulfofatty acids.

Suitable surfactants in the form of sulfates are the salts mentioned above of the sulfuric acid monoesters of the primary and secondary alcohols. It is also possible to use sulfated fatty acid monoglycerides and sulfated reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.

Of the carboxylates, sodium salts of neutral fatty acids, ie conventional soaps, are particularly suitable.

Preferred cationic surfactants are dialkyldimethylammonium chlorides such as distearyldimethylammonium chloride and imidazolinium salts in the form of methoxysulfonic acid 1-alkylaminoethyl-1-methyl-2-alkylimidazolinium.

Suitable amphoteric surfactants in the aqueous solution layer containing not only anions but also cationic groups in the same molecule are compounds of alkylbetaines or alkylsulfobetaines.

As nonionic surfactants, additions of 4 to 40, preferably 4 to 20 moles of ethylene oxide are advantageous for 1 mole of aliphatic alcohol, alkylphenol, fatty acid, aliphatic amine, fatty acid amide or alkylsulfonamide. In particular, addition products of 5 to 16 moles of ethylene oxide are preferred for the 8-18, preferably 12-18 primary or secondary alcohols and for the mono- or dialkyl-phenols having 6-14 carbon atoms in the alkyl radicals. Do. However, in addition to these water soluble nonionic surfactants, it is also possible to use insoluble or slightly water soluble polyglycol ethers having 1 to 4 ethylene glycol ether groups in the molecule, especially with water soluble nonionic or anionic surfactants.

Even more suitable nonionic surfactants include propylene glycol, alkylenediamine polypropylene glycol and alkylpolypropylene glycol having 1 to 1 carbon atoms in the alkyl chain containing 20 to 250 ethylene glycol ether groups and 10 to l00 propylene glycol ether groups. There are water-soluble addition products of ethylene oxide, wherein polypropylene glycol chains that act as hydrophobic groups are also preferred.

Suitable bleaches are in particular sodium perborate tetrahydrate, (NaBO ₂ x H ₂ O ₂ x 3H ₂ O), sodium perborate monohydrate (NaBO ₂ x H ₂ O ₂ ), perborate (Na ₂ B ₄ O ₇ x Peroxy compounds such as 4H ₂ O ₂ ) or peroxycarbonates such as Na ₂ CO ₃ x 1.5H ₂ O ₂ , as well as inorganic or organic active chlorine compounds such as alkali metal hypochlorite or dichloro and trichloro-cyanuric acid .

In general, it is advantageous to combine with a peroxy bleach material to stabilize the peroxy compound. Water-soluble stabilizers include organic teas suitable as an adjuvant for bonding light water ions Ca ²⁺ and Mg ²⁺ . Particular preference is given to insoluble stabilizers using magnesium silicate MgO: SiO ₂ in a ratio of from 0.5 to 4% by weight of the total formulation in the composite, between 4: 1 and 1: 4, preferably between 2: 1 and 1: 2. .

Activators used for bleaches that provide H ₂ O ₂ in water include N-diasylated and N, N′-tetraacylated amines. Eg, N, N, N ', N'-tetraacetylmethylenediamine or -ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluidine, N-methyl-N-mesylacetamide, Alkyl-N-sulfonylcarboxyamides, such as N-methyl-N-mesylbenzamide, N-acylated cyclic hydrazides, acylated triazoles or azoles such as monoacetylmaleiodrazide, O-benzoyl -N, N-succinylhydroxylamine, O-acetyl -N, N-succinylhydroxylamine, Op-methoxybenzoyl-N, N-succinylhydroxylamine, Op-nitrobenzoyl-N, N- O, N, N-trisubstituted hydroxylamines, such as succinylhydroxylamine and O, N, N-triacetylhydroxylamine, N, N'- diacylsulfurylamide, such as N, N'-dimethyl- N, N'-diacetylsulfurylamide and N, N'-diethyl-N, N'-dipropionylsulfurylamide, cyanuric triacyl, benzoic anhydride, such as cyanuric triacetyl or tribenzoyl, m-claw Benzoic anhydride, phthalic anhydride and 4-chloro phthalic anhydride, sugar esters such as pentaacetic acid glucose, 1, 3-diformyl-4,5-diacetoxyimidizolidine, 1, 3-diacetyl-4, 5-diacetoxyimidazolidine and 1, 3-diacetyl-4,5-dipropionyloxyimidazolidine, diacylated 2, 5-diketopiperazine, for example 1, 4-di Acetyl-2, 5-diketopiperazine, 1, 4-dipropionyl-2, 5-diketopiperazine and 1, 4-dipropionyl-3, 6-dimethyl-2, 5-diketopipera Gin, sodium salt of p- (ethoxycarbonyloxy) benzoic acid and p- (propoxycarbonyloxy) benzosulfonic acid and p-acetoxybenzenesulfoic acid, 2-acetoxy-5-nonylbenzene-sulfonic acid, 2- Sodium salts of alkylated or acylated phenolsulfonic esters such as acetoxy-5-propylbenzenephonic acid or isononanoyloxyphenyl sulfonic acid.

A gray inhibitor is a reattachment inhibitor that keeps falling off in suspension in an aqueous solution. Suitable for this purpose are organic water soluble colloids. Preferred are water-soluble salts of polymeric carboxylic acids, salts of ether carboxylic acids or ethylsulphonic acids of starch or salts of cellulose and sulfuric acid ester salts of cellulose or starch. It is also possible to use water-soluble polyamides and polyvinylpyrrolidones containing acid groups.

Possible enzymes in the composition include proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases and nucleases. Of particular interest are enzymes, especially proteases and amylases, obtained from bacteriostatic strains or bacteria, such as Bacillus subtilis or atreptomyces griseus, which are alkali, oligomeric and anionic interfaces. It is relatively resistant to active agents and still active below 70 ° C.

Preference is given to using enzyme combinations of various functions, in particular combinations of proteases and amylases. Complex-cleaners often and advantageously contain fluorescent bleaches. As for cotton, diaminostilbenesulfonic acid derivatives or alkali metal salts thereof, such as 4, 4'-bis (2-anilino-4-morpholino-1, 3, 5-trijin-6-ylamino) Alkali metal salts of stilbene-2 and 2'-disulfonic acid are obtained by using 1, 3-diaryl-2-pyrazoline for polyamide fibers, i.e., 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl Preference is given to using))-2-pyrazolyl and 2, 5-di (5-methyl-2-benzoxazolyl) ethylene for polyester fibers.

Alkaline cleaners generally contain sodium silicate and potassium silicate having a silicon dioxide / alkali-oxide ratio greater than 1 as a disinfectant.

Examples of the immersion component suitable for the cleaning agent include, in particular, alkali substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and alkali salts of orthophosphoric acid, sodium silicate having a silicon dioxide / alkali oxide metal ratio of 0.7 to 1.5. And potassium silicates, and also organic or inorganic acids such as hydrochloric acid, phosphoric acid, phosphate esters, sulfuric acid, oxalic acid, citric acid, formic acid, sulfamic acid, adipic acid, glutaric acid or succinic acid.

The cleaning and cleaning agent according to the invention can be a powder or a liquid. Inorganic salts, in particular sodium sulphate, are generally added to give powder formulations such properties as free flow and absence of aggregates at various atmospheric humidity, while water is the basis for most liquid formulations.

Especially preferred are cleaning agents containing 10-30% by weight zeolite and 5-15% by weight trisodium salt of β-alanine-N, N-diacetic acid, based on the total formulation.

The cleaning and cleaning agents according to the invention can be prepared in a conventional manner; For example, various components are kneaded with water to form an aqueous slurry, which is then advantageously spray dried at 100 ° C. at the tip.

Examples I1 to I5 of the present invention and Comparative Examples C1 to C5.

Removed the cured deposits formed using various cleaning agents.

For this purpose, 20 sheets of cotton terry towel cloth are repeatedly washed and rinsed with a test fabric under the following experimental conditions.

Washing machine Launder-O-meter from Chicago, Atlas

Washing cycle recovery amount of water / circulation

20

125ml wash

125 ml for rinsing

Total water strength 4 mmol (Ca ²⁺ , Mg ²⁺ )

Cleaning time / circulation 30 minutes

60 ℃ cleaning time

Cleanser Dose 8g / L

The cleaning agents used in Examples Il to I5 of the present invention contain trisodium salts of β-alanine-N, N-diacetic acid (ADA) to be used according to the present invention, while in Comparative Examples C1 to C5 ADA is used herein. Replace with the trisodium salt of nitrilotriacetic acid (NTA) shown. In all cases, the cleaning agents are prepared by spray drying the aqueous slurry of the individual components to 100 ° C. in the tower. The weight of the cured deposits formed during washing is the weight ratio of ash.

The ash composition of the detergent used and the weight ratio obtained are shown in Table 1. In addition, Table 1 contains the complete ionic composition of the total hard water used, which is changed as an additional factor.

TABLE 1

Claims (3)

An aqueous cleaning or cleaning agent containing from 2 to 25% by weight of β-alanine-N, N-diacetic acid or an alkali metal or an ammonium salt thereof as a softener of water based on the total weight of the cleaning or cleaning agent. The aqueous washing or cleaning agent according to claim 1, which contains a trisodium salt of β-alanine-N or N-diacetic acid as a softener of water. The cleaning agent according to claim 1, which contains 10 to 30% by weight of zeolite and 5 to 15% by weight of β-alanine-N, N-diacetic acid trisodium salt.